EP0902737B1 - Cellule electrochimique de configuration ouverte, a couche mince flexible - Google Patents

Cellule electrochimique de configuration ouverte, a couche mince flexible Download PDF

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Publication number
EP0902737B1
EP0902737B1 EP96940909A EP96940909A EP0902737B1 EP 0902737 B1 EP0902737 B1 EP 0902737B1 EP 96940909 A EP96940909 A EP 96940909A EP 96940909 A EP96940909 A EP 96940909A EP 0902737 B1 EP0902737 B1 EP 0902737B1
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EP
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Prior art keywords
cell
layer
insoluble
layers
powder
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EP96940909A
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German (de)
English (en)
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EP0902737B9 (fr
EP0902737A1 (fr
EP0902737A4 (fr
Inventor
Zvi Nitzan
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Power Paper Ltd
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Power Paper Ltd
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    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61B—DIAGNOSIS; SURGERY; IDENTIFICATION
    • A61B5/00—Measuring for diagnostic purposes; Identification of persons
    • A61B5/145—Measuring characteristics of blood in vivo, e.g. gas concentration, pH value; Measuring characteristics of body fluids or tissues, e.g. interstitial fluid, cerebral tissue
    • A61B5/14532—Measuring characteristics of blood in vivo, e.g. gas concentration, pH value; Measuring characteristics of body fluids or tissues, e.g. interstitial fluid, cerebral tissue for measuring glucose, e.g. by tissue impedance measurement
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B3/00—Layered products comprising a layer with external or internal discontinuities or unevennesses, or a layer of non-planar form; Layered products having particular features of form
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61N—ELECTROTHERAPY; MAGNETOTHERAPY; RADIATION THERAPY; ULTRASOUND THERAPY
    • A61N1/00—Electrotherapy; Circuits therefor
    • A61N1/18—Applying electric currents by contact electrodes
    • A61N1/20—Applying electric currents by contact electrodes continuous direct currents
    • A61N1/30—Apparatus for iontophoresis, i.e. transfer of media in ionic state by an electromotoric force into the body, or cataphoresis
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B65—CONVEYING; PACKING; STORING; HANDLING THIN OR FILAMENTARY MATERIAL
    • B65D—CONTAINERS FOR STORAGE OR TRANSPORT OF ARTICLES OR MATERIALS, e.g. BAGS, BARRELS, BOTTLES, BOXES, CANS, CARTONS, CRATES, DRUMS, JARS, TANKS, HOPPERS, FORWARDING CONTAINERS; ACCESSORIES, CLOSURES, OR FITTINGS THEREFOR; PACKAGING ELEMENTS; PACKAGES
    • B65D51/00—Closures not otherwise provided for
    • B65D51/24—Closures not otherwise provided for combined or co-operating with auxiliary devices for non-closing purposes
    • B65D51/248—Closures not otherwise provided for combined or co-operating with auxiliary devices for non-closing purposes the closure being provided with transient audible or visual signaling means, e.g. for indicating dispensing, or other illuminating or acoustic devices, e.g. whistles
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/04—Construction or manufacture in general
    • H01M10/0436—Small-sized flat cells or batteries for portable equipment
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/06—Lead-acid accumulators
    • H01M10/12—Construction or manufacture
    • H01M10/126—Small-sized flat cells or batteries for portable equipment
    • H01M10/127—Small-sized flat cells or batteries for portable equipment with bipolar electrodes
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M6/00—Primary cells; Manufacture thereof
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M6/00—Primary cells; Manufacture thereof
    • H01M6/04—Cells with aqueous electrolyte
    • H01M6/06—Dry cells, i.e. cells wherein the electrolyte is rendered non-fluid
    • H01M6/12—Dry cells, i.e. cells wherein the electrolyte is rendered non-fluid with flat electrodes
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M6/00—Primary cells; Manufacture thereof
    • H01M6/14—Cells with non-aqueous electrolyte
    • H01M6/18—Cells with non-aqueous electrolyte with solid electrolyte
    • H01M6/181—Cells with non-aqueous electrolyte with solid electrolyte with polymeric electrolytes
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M6/00—Primary cells; Manufacture thereof
    • H01M6/22—Immobilising of electrolyte
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M6/00—Primary cells; Manufacture thereof
    • H01M6/40—Printed batteries, e.g. thin film batteries
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M2300/00—Electrolytes
    • H01M2300/0002—Aqueous electrolytes
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M2300/00—Electrolytes
    • H01M2300/0002—Aqueous electrolytes
    • H01M2300/0014—Alkaline electrolytes
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M2300/00—Electrolytes
    • H01M2300/0085—Immobilising or gelification of electrolyte
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
    • H01M4/621—Binders
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
    • H01M50/50—Current conducting connections for cells or batteries
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M6/00—Primary cells; Manufacture thereof
    • H01M6/42—Grouping of primary cells into batteries
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M6/00—Primary cells; Manufacture thereof
    • H01M6/42—Grouping of primary cells into batteries
    • H01M6/46—Grouping of primary cells into batteries of flat cells
    • H01M6/48—Grouping of primary cells into batteries of flat cells with bipolar electrodes
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10—Energy storage using batteries
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
    • Y02P70/50—Manufacturing or production processes characterised by the final manufactured product
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/24—Structurally defined web or sheet [e.g., overall dimension, etc.]
    • Y10T428/24802—Discontinuous or differential coating, impregnation or bond [e.g., artwork, printing, retouched photograph, etc.]
    • Y10T428/24917—Discontinuous or differential coating, impregnation or bond [e.g., artwork, printing, retouched photograph, etc.] including metal layer
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/24—Structurally defined web or sheet [e.g., overall dimension, etc.]
    • Y10T428/24802—Discontinuous or differential coating, impregnation or bond [e.g., artwork, printing, retouched photograph, etc.]
    • Y10T428/24926—Discontinuous or differential coating, impregnation or bond [e.g., artwork, printing, retouched photograph, etc.] including ceramic, glass, porcelain or quartz layer

Definitions

  • the present invention relates to electrochemical cells which are used as battery power sources by converting chemical energy to electrical energy. More particularly, the present invention relates to a primary or rechargeable electrochemical cell to be used as a regular or rechargeable battery which accomplishes the conversion of chemical energy to electrical energy using a wet (e.g., liquid state) electrolyte, yet maintain a flexible thin layer and open configuration.
  • a wet e.g., liquid state
  • Batteries can be broadly classified into two categories in which the batteries of the first category include wet electrolytes (i.e., liquid state batteries), whereas batteries of the second category include solid state electrolyte.
  • solid state batteries have an inherent advantage, they do not dry out and do not leak, they suffer major disadvantages when compared with liquid state batteries since, due to limited diffusion rates of ions through a solid, their operation is temperature dependent to a much larger extent, and many operate well only under elevated temperatures; and, the limited diffusion rates thus described, characterize solid state batteries with low ratio of electrical, energy generated. vs. their potential chemical energy.
  • Liquid state thin layer batteries typically include a positive and negative active insoluble material layer put together with a separator interposed therebetween, which separator is soaked with a liquid electrolyte solution, thus functioning as an electrolytic liquid layer.
  • Such batteries an example of which is disclosed for example in U.S. Pat. No. 4,623,598 to Waki et al. , and in Japanese Pat. No. JP 61-55866 to Fuminobu et al. , have to be sealed within a sheathing film to prevent liquid evaporation, and are therefore closed electrochemical cells.
  • European patent specification no. EP 0 456 122 discloses a galvanic Leclanche type cell.
  • a transdermal therapeutic system is disposed which is built up in layers and has an electrically insulating backing layer which is impermeable to active substance, and two galvanic elements which are arranged in a manner insulated from one another.
  • the skin-side electrodes of the galvanic elements bear layers and the layer of at least one of the skin-side electrodes contains a pharmaceutical active substance. Moisture may diffuse into the cell at activation.
  • EP 0 456 122 does not disclose a galvanic cell including a deliquescent material to keep the cell wet at all times.
  • an open electrochemical cell which can be used as a primary or rechargeable power supply for various miniaturized and portable electrically powered devices of compact design.
  • a method of manufacturing such a cell includes a wet electrolyte, yet maintains a flexible, thin and open configuration, thus devoid of accumulation of gases upon storage.
  • the cell comprising a first layer of insoluble negative pole, a second layer of insoluble positive pole and a third layer of aqueous electrolyte, the third layer being disposed between the first and second layers and including: (a) a deliquescent material for keeping the open cell wet at all times; (b) an electroactive soluble material for obtaining required ionic conductivity; and, (c) a watersoluble polymer for obtaining a required viscosity for adhering the first and second layers to the third layer.
  • the electrolyte layer is engaged by a porous substance.
  • the porous substance is selected from the group consisting of a filter paper, a plastic membrane, a cellulose membrane and a cloth.
  • the first layer of insoluble positive pole includes manganese-dioxide powder and the second layer of insoluble negative pole includes zinc powder.
  • the first layer of insoluble negative pole and/or the second layer of insoluble positive pole further includes carbon powder and the electroactive soluble material is selected from the group consisting of zinc-chloride, zinc-bromide, zinc-fluoride and potassium-hydroxide.
  • the first layer of insoluble negative pole includes silver-oxide powder and the second layer of insoluble positive pole includes zinc powder and the electroactive soluble material is potassium-hydroxide.
  • the first layer of insoluble negative pole includes cadmium powder and the second layer of insoluble positive pole includes nickel-oxide powder and the electroactive soluble material is potassium-hydroxide.
  • the first layer of insoluble negative pole includes iron powder and the second layer of insoluble positive pole includes nickel-oxide powder and the electroactive soluble material is potassium-hydroxide.
  • the first layer of insoluble negative pole and the second layer of insoluble positive pole include lead-oxide powder, the cell is charged by voltage applied to the poles and the electroactive soluble material is sulfuric-acid.
  • the deliquescent material and the electroactive soluble material are the same material and are selected from the group consisting of zinc-chloride, zinc-bromide, zinc-fluoride and potassium-hydroxide.
  • the deliquescent material is selected from the group consisting of calcium-chloride, calcium-bromide, potassium-biphosphate and potassium-acetate.
  • the watersoluble polymer is selected from the group consisting of polyvinylalcohol, poliacrylamide, polyacrylic acid, polyvinylpyrolidone, polyethylenoxide, agar, agarose, starch, hydroxyethylcellulose and combinations and copolymers thereof.
  • the watersoluble polymer and the deliquescent material are the same material and are selected from the group consisting of dextrane, dextranesulfate and combinations and copolymers thereof.
  • the cell further comprising terminals, each of the terminals being in electrical contact with one of the first and second pole layers.
  • the terminal are made of graphite or a metal.
  • the metal is selected from the group consisting of iron, nickel, titanium, copper, stainless steel and mixtures thereof, and the terminals are applied to the cell by a suitable printing technology such as, but not limited to, silk print, offset print, jet printing, lamination, materials evaporation or powder dispersion.
  • the cell further comprising at least one conductive layer improving the electronic conductivity of at least one of the first and second pole layers.
  • the conductive layer is selected from the group consisting of a graphite paper and carbon cloth.
  • the cell further comprises an external layer selected from the group consisting of an adhesive backing layer, a lamina protective layer and a combination of adhesive backing layer and a lamina protective layer.
  • an electrical power supply comprising at least two cells featured as above, the cells are connected in a head to tail orientation in a bipolar-connection.
  • connection is by an adhesive selected from the group consisting of a conductive double sided adhesive tape and a conductive glue layer.
  • the conductive double sided adhesive tape and the conductive glue layer are applied by a printing technology.
  • the cell comprises a first layer of insoluble negative pole, a second layer of insoluble positive pole and a third layer of aqueous electrolyte, the third layer being disposed between the first and second layers and including: (a) a watersoluble polymer for obtaining a required viscosity for adhering the first and second layers to the third layer and for obtaining a required hygroscopicality for keeping the open cell wet at all times; and (b) an electroactive soluble material for obtaining a required ionic conductivity.
  • the method of making an open electrochemical cell comprises the steps of (a) wetting a porous substance having a first side and a second side with an aqueous solution containing a deliquescent material, an electroactive soluble material and a watersoluble polymer; (b) applying onto the first side a layer of negative pole; and (c) applying onto the second side a layer of positive pole.
  • the wetting is by a dipping or printing technologies.
  • the layers of negative and positive poles include active insoluble powder materials mixed with the deliquescent material, electroactive soluble material and watersoluble polymer, the application of the layers of negative and positive poles is by a printing technology.
  • the present invention successfully addresses the shortcomings of the presently known configurations by providing a flexible thin layer open electrochemical cell which does not accumulate gases upon storage, yet it is maintained wet and intact by the use of a deliquescent material for keeping it wet at all times and a watersoluble polymer for obtaining the required viscosity for adhering the pole layers to the aqueous electrolyte layer.
  • Further qualities of the cell include having no outer rigid casting therefore it is thin light and flexible and may be manufactured in any size, shape, color and applied patterns, hence it is suitable for a variety of applications; cost effectiveness; made of environmental and human friendly materials; and, self sticking via an adhesive backing.
  • the present invention is of a flexible thin layer open electrochemical cell which can be used as a primary or rechargeable power supply for various miniaturized and portable electrically powered devices of compact design.
  • the flexible thin layer open electrochemical cell of the present invention includes a wet electrolyte, yet maintains a flexible, thin and open configuration, thus devoid of accumulation of gases upon storage.
  • Figure 1 illustrates a basic configuration of the flexible thin layer open electrochemical cell of the present invention, generally designated 10.
  • Cell 10 includes three layers as follows.
  • on discharged negative pole is where an oxidation occurs, whereas the positive pole is where reduction occurs.
  • the aqueous electrolyte layer 12 includes a deliquescent (i.e., hygroscopic) material for keeping open cell 10 wet at all times; an electroactive soluble material for obtaining the required ionic conductivity; and a watersoluble polymer for obtaining the required viscosity for adhering pole layers 14 and 16 to aqueous electrolyte layer 12.
  • a deliquescent (i.e., hygroscopic) material for keeping open cell 10 wet at all times
  • an electroactive soluble material for obtaining the required ionic conductivity
  • a watersoluble polymer for obtaining the required viscosity for adhering pole layers 14 and 16 to aqueous electrolyte layer 12.
  • the aqueous electrolyte layer 12 typically includes a porous insoluble substance, such as but not limited to, filter paper, plastic membrane, cellulose membrane, cloth, etc., the porous substance is wetted by an aqueous solution including three components: a deliquescent material, an electroactive soluble material; and a watersoluble polymer.
  • the deliquescent material by being hygroscopic maintains cell 10 moisturized at all times.
  • the level of moisture within open cell 10 may vary depending on deliquescent material selection, its concentration and air humidity.
  • Suitable deliquescent materials include, but are not limited to, calcium-chloride, calcium-bromide, potassium-biphosphate, potassium-acetate and combinations thereof.
  • the electroactive soluble material is selected in accordance with the materials of which the negative and positive pole layers are made.
  • a list of frequently used electro active soluble materials suitable for the present invention includes for example zinc-chloride, zinc-bromide and zinc-fluoride for various primary cells and potassium-hydroxide and sulfuric-acid for rechargeable cells.
  • the watersoluble polymer is employed as an adhesive agent to adhere (i.e., glue) pole layers 14 and 16 to the aqueous electrolyte layer 12.
  • adhesive agent i.e., glue
  • polymers are suitable ones, such as for example polyvinylalcohol, poliacrylamide, polyacrylic acid, polyvinylpyrolidone, polyethylenoxide, agar, agarose, starch, hydroxyethylcellulose and combinations and copolymers thereof.
  • Each of negative and positive pole layers 14 and 16 includes a mix of a suitable (negative or positive, respectively) active insoluble powder material with an aqueous solution similar to the solution described hereinabove, including a deliquescent material; an electroactive soluble material; and a watersoluble polymer.
  • the deliquescent material and the watersoluble polymer may be selected otherwise in the later solution, in other words, the electroactive soluble material should be kept the same in all three layers 12, 14 and 16, whereas the deliquescent material and the watersoluble polymer may be varied between layers according to the specific application.
  • Appropriate selection of active insoluble powder materials for the negative 14 and positive 16 pole layers with a matching electroactive soluble material provides flexible thin layer cell 10 which can be used as a power supply (i.e., a battery), which cell 10 is open and therefore does not accumulate gases upon storage, yet the hygroscopicality of the deliquescent material ensures that cell 10 is kept wet at all times although open.
  • a power supply i.e., a battery
  • Suitable pairs of materials to be used in negative 14 and positive 16 poles include, but are not limited to, manganese-dioxide/zinc; silver-oxide/zinc; cadmium/nickel-oxide; and iron/nickel-oxide (the manganese-dioxide and the silver-oxide are optionally mixed with a conductive carbon powder as known in the art).
  • a single material may function both as a deliquescent material and as the electroactive soluble material. Such a material should however acquire suitable electroactive and hygroscopic characteristics. Suitable materials of this type include, but are not limited to, zinc-chloride and zinc-bromide.
  • a single material may function as a deliquescent material and as a watersoluble polymer. Such a material should however acquire suitable hygroscopic and adhesivness characteristics. Suitable materials of this type include, but are not limited to, dextrane, dextranesulfate and combinations and copolymers thereof.
  • cell 10 is flexible and as thin as 0.5-1.5 mm or less. It is presently preferred and will be further detailed below that cell 10 will be manufactured by a suitable printing technology. Suitable printing technologies include, but are not limited to, silk print, offset print, jet printing, lamination, materials evaporation and powder dispersion.
  • cell 20 also includes layers 12, 14 and 16 (stripped region) forming a basic cell.
  • Cell 20 further includes additional one or two conductive layers 22 and 24, to improve the electronic conductivity of negative 14 and/or positive 16 pole layers. Suitable conductive layers are graphite paper, carbon cloth, etc.
  • Cell 20 also includes negative 26 and positive 28 terminals, which terminals 26 and 28 are in electrical contact with either the corresponding pole layer 14 and 16, respectively, or with the corresponding conductive layer 22 and 24, respectively, or both.
  • Terminals 26 and 28 are made of any suitable materials such as, but not limited to, graphite or metals such as iron, nickel, titanium, copper, stainless steel and mixtures thereof, and are preferably applied to cell 20 by a suitable printing technology such as the ones listed above. Terminals 26 and 28 are used to electrically connect cell 20 to a load such as an electrically powered device. Terminals 26 and 28 may be located in any desired location of cell 20, may acquire any suitable shape and size and, depending on the specific application, terminals 26 and 28 may protrude from the surface of cell 20. Cell 20 may further include at least one externally located adhesive backing 29, to enable attaching cell 20 to various surfaces, and/or at least one externally located lamina protective layer 30 to physically protect all other layers.
  • Two or more cells 10, as shown in Figure 3a, or cells 20, as shown in Figure 3b, may be electrically connected by a bi-polar connection to additively increase the electrical energy obtained of thus formed electrical power supplies 40 and 50, respectively.
  • two or more cells are adhered to one another in a head to tail orientation, as indicated in Figures 3a-b by layers 22, 14, 12, 16 and 24 arrangement, by a conductive double sided adhesive tape, or a conductive glue layer 42 applied for example by a suitable printing technology, enabling passage of electrons between adjacent cells.
  • electrical power supplies 40 and/or 50 may further include externally located adhesive backing(s) similar to surface 29 of Figure 2 and/or externally located lamina protective layer(s), similar to layer 30 of Figure 2. It is further clear that electrical power supplies 40 and 50 may include a negative and a positive terminal similar to terminals 26 and 28, respectively, of Figure 2.
  • the present invention further includes a method of making a flexible thin layer open liquid state electrochemical cells similar to the cells described above, the method includes the steps of (a) wetting a porous substance an aqueous solution containing a deliquescent material, an electroactive soluble material and a watersoluble polymer; wetting may be achieved by either dipping or printing technologies; (b) applying onto one side of the porous substance a negative pole layer; and, (c) applying onto the second side of the porous substance a positive pole layer.
  • the negative and positive pole layers include active insoluble powder substances mixed with the deliquescent material, electroactive soluble material and watersoluble polymer preferably of the same types as under (a), and are preferably applied using a suitable printing technology selected for example from the ones listed above.
  • the method may further include adding to the cell additional layers and parts, such as but not limited to, externally located adhesive backing(s) and/or lamina protective layer(s), and negative and a positive terminals.
  • the method may further include bi-polar joining of two or more cells, for example with a conductive double sided adhesive tape or a conductive glue layer applied for example by a suitable printing technology, to form a power supply with an increased power (e.g., substantially doubled, tripled, etc.).
  • bi-polar joining may be performed by joining together in a head to tail orientation two or more premanufactured cells, or alternatively, directly manufacturing two or more cells thus oriented, by applying suitable layer one after the other, preferably using a suitable printing technology as described above.
  • the flexible thin layer open electrochemical cell of the present invention has a major advantage over prior art thin layer cells. Since it is an open cell it does not accumulate gases upon storage, yet it is maintained wet and intact by the use of a deliquescent material for keeping it wet at all times and a watersoluble polymer for obtaining the required viscosity for adhering the pole layers to the aqueous electrolyte layer.
  • the flexible thin layer open electrochemical cell of the present invention has other qualities as follows. First, it has no outer rigid casting therefore it is thin light and flexible and may be manufactured in any size, shape, color and applied patterns, hence it is suitable for a variety of applications. Second, by using a suitable printing technology for its manufacturing its cost is reduced and therefore it may be disposed after use partly since large sheets can be produced and cut to any desired size following printing and partly since this technology is inherently cost effective. Third, it is preferably made of environmental and human friendly materials (it preferably contains no mercury or heavy metals). And finally, it may be manufactured self sticking via an adhesive backing.
  • a solution containing 120 mg of polyvinylalcohol (an aqueous soluble polymer) and 1680 mg of zinc-chloride (a deliquescent material and an electroactive soluble material) in 1.2 ml of water was prepared. This solution had a glue like viscous appearance. A 4.5 cm x 7 cm strip of a filter paper was thoroughly wetted with this solution by a printing or dipping technologies. A mixture of 300 mg zinc powder with the above solution was prepared and was printed on one side of the paper strip serving as the negative pole layer. On the other side printed was a mixture of 250 mg manganese-dioxide and 50 mg of a conductive carbon powder, together with the above solution, serving as the positive pole layer. When electrical contacts were made with both sides and were connected over a load an electrical current was measured. A current of 12 microampers per cm 2 at a voltage of 1.7 ⁇ 1.2 volts was easily maintained for five days continuously under room conditions.
  • a saturated potassium-hydroxide solution is prepared and brought to the viscosity of a glue by mixing with a water soluble polymer.
  • a porous substance e.g., a filter paper
  • a porous substance e.g., a filter paper
  • a mixture of the solution with nickel-oxide powder is pasted on one side of the porous substance to form a positive pole layer and, a similar mixture with cadmium powder is pasted on the other side of the porous substance to form a negative pole layer.
  • Example 3 The same potassium-hydroxide solution as in Example 3 is prepared and a porous substance is wetted with it. A mixture of the solution with zinc powder is pasted on one side of the porous substance to form a negative pole layer and a similar mixture with silver-oxide powder containing some carbon powder if so desired is pasted on the other side of the porous substance to form a positive pole layer. By connecting a voltmeter to the two sides a voltage of 1.2 volts is measured and appreciable current is measured when the two layers are contacted over a load. The cell does not dry out in the open and can be recharged if so desired.
  • the same potassium-hydroxide solution as in Example 3 is prepared and a porous substance is wetted with it.
  • a mixture of the solution with zinc powder is pasted on one side of the porous substance to form a negative pole layer and a similar mixture with manganese-dioxide powder containing some carbon powder if so desired is pasted on the other side of the porous substance to form a positive pole layer.
  • a voltage of 1.5 volts is measured and appreciable current is measured when the two layers are contacted over a load. The cell does not dry out in the open. Recharging thus formed cell may be troublesome.
  • Example 3 The same potassium-hydroxide solution as in Example 3 is prepared and a porous substance is wetted with it. A mixture of the solution with nickel-oxide powder is pasted on one side of the porous substance to form a positive pole layer and a similar mixture with iron powder is pasted on the other side of the porous substance to form a negative pole layer. By connecting a voltmeter to the two sides a voltage of 0.9 volts is measured and a current can be measured when the two layers are contacted over a load. The cell does not dry out in the open and some recharged is possible if so desired.
  • a 30% sulfuric acid solution is prepared and brought to the viscosity of a glue by mixing with a water soluble polymer.
  • a porous substance e.g., a filter paper
  • a mixture of the solution with lead-oxide is pasted on both sides of the porous substance. Both sides are connected to a power supply and a voltage higher than 2 volts is applied by which the cell is charged. Charge and discharge cycles can be repeated without the cell drying out in the open.

Claims (40)

  1. Pile électrochimique de configuration ouverte comprenant une première couche constituant un pôle négatif insoluble, une deuxième couche constituant un pôle positif insoluble et une troisième couche constituant un électrolyte liquide, ladite troisième couche étant disposée entre lesdites première et deuxième couches et englobant :
    (a) une matière déliquescente pour maintenir la pile de configuration ouverte liquide à tout moment ;
    (b) une matière soluble électroactive pour obtenir la conductivité ionique requise ; et
    (c) un polymère hydrosoluble pour obtenir une viscosité requise pour l'adhérence desdites première et deuxième couches à ladite troisième couche.
  2. Pile selon la revendication 1, dans laquelle ladite couche faisant office d'électrolyte est mise en contact avec une substance poreuse.
  3. Pile selon la revendication 2, dans laquelle ladite substance poreuse est choisie parmi le groupe constitué par un papier filtre, une membrane plastique, une membrane cellulosique et une étoffe.
  4. Pile selon la revendication 1, dans laquelle ladite première couche constituant un pôle négatif insoluble englobe de la poudre de dioxyde de manganèse et ladite deuxième couche constituant un pôle positif insoluble englobe de la poudre de zinc.
  5. Pile selon la revendication 4, dans laquelle ladite première couche constituant un pôle négatif insoluble englobe de la poudre de carbone.
  6. Pile selon la revendication 4, dans laquelle ladite deuxième couche constituant un pôle positif insoluble englobe en outre de la poudre de carbone.
  7. Pile selon la revendication 4, dans laquelle ladite matière électroactive soluble est choisie parmi le groupe constitué par le chlorure de zinc, le bromure de zinc, le fluorure de zinc et l'hydroxyde de potassium.
  8. Pile selon la revendication 1, dans laquelle ladite première couche constituant un pôle négatif insoluble englobe de la poudre d'oxyde d'argent et ladite deuxième couche constituant un pôle positif insoluble englobe de la poudre de zinc.
  9. Pile selon la revendication 8, dans laquelle ladite matière électroactive soluble est de l'hydroxyde de potassium.
  10. Pile selon la revendication 1, dans laquelle ladite première couche constituant un pôle négatif insoluble englobe de la poudre de cadmium et ladite deuxième couche constituant un pôle positif insoluble englobe de la poudre d'oxyde de nickel.
  11. Pile selon la revendication 10, dans laquelle ladite matière électroactive soluble est de l'hydroxyde de potassium.
  12. Pile selon la revendication 1, dans laquelle ladite première couche constituant un pôle négatif insoluble englobe de la poudre de fer et ladite deuxième couche constituant un pôle positif insoluble englobe de la poudre d'oxyde de nickel.
  13. Pile selon la revendication 12, dans laquelle ladite matière électroactive soluble est de l'hydroxyde de potassium.
  14. Pile selon la revendication 1, dans laquelle ladite première couche constituant un pôle négatif insoluble et ladite deuxième couche constituant un pôle positif insoluble englobent de la poudre d'oxyde de plomb, la pile étant chargée en appliquant une tension auxdites bornes.
  15. Pile selon la revendication 14, dans laquelle ladite matière électroactive soluble est de l'acide sulfurique.
  16. Pile selon la revendication 1, dans laquelle ladite matière déliquescente et ladite matière électroactive soluble représentent la même matière.
  17. Pile selon la revendication 16, dans laquelle ladite même matière est choisie parmi le groupe constitué par du chlorure de zinc, du bromure de zinc, du fluorure de zinc et de l'hydroxyde de potassium.
  18. Pile selon la revendication 1, dans laquelle ladite matière déliquescente est choisie parmi le groupe constitué par le chlorure de calcium, le bromure de calcium, le diphosphate de potassium et l'acétate de potassium.
  19. Pile selon la revendication 1, dans laquelle ledit polymère hydrosoluble est choisi parmi le groupe constitué par l'alcool polyvinylique, le polyacrylamide, l'acide polyacrylique, la polyvinylpyrrolidone, l'oxyde de polyéthylène, la gélose, l'agarose, l'amidon, l'hydroxyéthylcellulose ainsi que leurs combinaisons et leurs copolymères.
  20. Pile selon la revendication 1, dans laquelle ledit polymère hydrosoluble et ladite matière déliquescente représentent la même matière.
  21. Pile selon la revendication 1, dans laquelle ladite matière est choisie parmi le groupe constitué par le dextran, le sulfate de dextran ainsi que leurs combinaisons et leurs copolymères.
  22. Pile selon la revendication 1, comprenant en outre des bornes, chacune desdites bornes étant mise en contact électrique avec une desdites première et deuxième couche faisant office de pôles.
  23. Pile selon la revendication 22, dans laquelle lesdites bornes sont réalisées en métal.
  24. Pile selon la revendication 22, dans laquelle lesdites bornes sont réalisées en graphite.
  25. Pile selon la revendication 23, dans laquelle ledit métal est choisi parmi le groupe constitué par le fer, le nickel, le titane, le cuivre, l'acier inoxydable et leurs mélanges, lesdites bornes étant appliquées sur la pile via une technologie d'impression.
  26. Pile selon la revendication 1, comprenant en outre au moins une couche conductrice améliorant la conductivité électronique d'au moins une desdites première et deuxième couches faisant office de pôles.
  27. Pile selon la revendication 26, dans laquelle ladite couche conductrice est choisie parmi le groupe constitué par du papier graphité et de l'étoffe carbonée.
  28. Pile selon la revendication 1, comprenant en outre une couche externe choisie parmi le groupe constitué par une couche dorsale adhésive, une couche de protection stratifiée et une combinaison d'une couche dorsale adhésive et d'une couche de protection stratifiée.
  29. Alimentation électrique comprenant deux piles selon la revendication 1, reliées dans une orientation de tête à queue dans un raccord bipolaire.
  30. Alimentation électrique selon la revendication 22, dans laquelle ledit raccord est réalisé à l'aide d'un adhésif choisi parmi le groupe constitué par un ruban adhésif conducteur double face et une couche de colle conductrice.
  31. Alimentation électrique selon la revendication 30, dans laquelle ledit ruban adhésif conducteur double face et ladite couche de colle conductrice sont appliqués via une technologie d'impression.
  32. Pile électrochimique de configuration ouverte comprenant une première couche constituant un pôle négatif insoluble, une deuxième couche constituant un pôle positif insoluble et une troisième couche constituant un électrolyte liquide, ladite troisième couche étant disposée entre lesdites première et deuxième couches et englobant :
    (a) un polymère hydrosoluble pour obtenir une viscosité requise pour l'adhérence desdites première et deuxième couches à ladite troisième couche et pour obtenir une hygroscopicité requise pour maintenir la pile de configuration ouverte liquide à tout moment ; et
    (b) une matière soluble électroactive pour obtenir la conductivité ionique requise.
  33. Procédé de fabrication d'une pile électrochimique de configuration ouverte, comprenant les étapes consistant à :
    (a) humidifier une substance poreuse possédant un premier côté et un deuxième côté avec une solution aqueuse contenant une matière déliquescente, une matière électroactive soluble et un polymère hydrosoluble ;
    (b) appliquer sur ledit premier côté une couche constituant un pôle négatif ; et
    (c) appliquer sur ledit deuxième côté une couche constituant un pôle positif.
  34. Procédé selon la revendication 33, dans lequel ladite humidification est mise en oeuvre via une technologie d'immersion.
  35. Procédé selon la revendication 33, dans lequel ladite humidification est mise en oeuvre via une technologie d'impression.
  36. Procédé selon la revendication 33, dans lequel lesdites couches constituant un pôle négatif et un pôle positif englobent des matières actives pulvérulentes insolubles mélangées avec ladite matière déliquescente, ladite matière électroactive soluble et ledit polymère hydrosoluble.
  37. Procédé selon la revendication 36, dans lequel ladite application desdites couches constituant un pôle négatif et un pôle positif est mise en oeuvre via une technologie d'impression.
  38. Pile selon la revendication 1, dans laquelle la couche faisant office d'électrolyte est mise en contact avec une substance poreuse flexible.
  39. Pile selon la revendication 1 ou selon la revendication 32, dans laquelle la pile est une pile flexible en couche mince.
  40. Pile selon la revendication 1 ou selon la revendication 32, dans laquelle l'électrolyte liquide comprend un électrolyte aqueux.
EP96940909A 1995-12-20 1996-11-29 Cellule electrochimique de configuration ouverte, a couche mince flexible Expired - Lifetime EP0902737B9 (fr)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
US08/575,190 US5652043A (en) 1995-12-20 1995-12-20 Flexible thin layer open electrochemical cell
US575190 1995-12-20
PCT/US1996/019048 WO1997022466A1 (fr) 1995-12-20 1996-11-29 Cellule electrochimique de configuration ouverte, a couche mince flexible

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EP0902737A1 EP0902737A1 (fr) 1999-03-24
EP0902737A4 EP0902737A4 (fr) 2004-08-04
EP0902737B1 true EP0902737B1 (fr) 2008-01-02
EP0902737B9 EP0902737B9 (fr) 2008-10-08

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EP (1) EP0902737B9 (fr)
JP (2) JP3512112B2 (fr)
KR (1) KR100412626B1 (fr)
CN (1) CN1088647C (fr)
AT (1) ATE382962T1 (fr)
AU (1) AU705251B2 (fr)
BR (1) BR9612226A (fr)
CA (1) CA2241012C (fr)
CZ (1) CZ195498A3 (fr)
DE (1) DE69637394T2 (fr)
ES (1) ES2300108T3 (fr)
HU (1) HUP0001187A3 (fr)
IL (1) IL124986A0 (fr)
PL (1) PL182732B1 (fr)
TR (1) TR199801149T2 (fr)
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CA2241012C (fr) 2005-11-15
US5811204A (en) 1998-09-22
JP2003297374A (ja) 2003-10-17
KR100412626B1 (ko) 2004-04-17
JP2000502206A (ja) 2000-02-22
HUP0001187A2 (hu) 2001-06-28
EP0902737B9 (fr) 2008-10-08
KR20000064499A (ko) 2000-11-06
USRE39676E1 (en) 2007-06-05
CZ195498A3 (cs) 1999-04-14
AU705251B2 (en) 1999-05-20
IL124986A0 (en) 1999-01-26
DE69637394T2 (de) 2009-01-02
BR9612226A (pt) 1999-12-28
TR199801149T2 (xx) 1998-08-21
JP3512112B2 (ja) 2004-03-29
EP0902737A1 (fr) 1999-03-24
CA2241012A1 (fr) 1997-06-26
PL327183A1 (en) 1998-11-23
ATE382962T1 (de) 2008-01-15
DE69637394D1 (de) 2008-02-14
ES2300108T3 (es) 2008-06-01
HUP0001187A3 (en) 2004-03-01
AU1085797A (en) 1997-07-14
PL182732B1 (pl) 2002-02-28
JP4309159B2 (ja) 2009-08-05
EP0902737A4 (fr) 2004-08-04
CN1088647C (zh) 2002-08-07
CN1207703A (zh) 1999-02-10
US5652043A (en) 1997-07-29

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